KR20240027755A - Fluoropolyether-based curable compositions and cured products, and electrical/electronic components - Google Patents

Abstract

(A) a perfluoropolyether compound having two or more alkenyl groups in one molecule, (B) a fluorinated organohydrogensilane compound represented by the following general formula (1) and having two or more hydrosilyl groups, (Rf) has a monovalent perfluoropolyether group, A is a divalent organic group, R is a monovalent hydrocarbon group, y is 1 or 2.) (C) A fluoropolyether-based curable composition containing a platinum group metal catalyst has durability against hydrofluoric acid or an electrolyte solution for lithium ion batteries, and the There are no uncured areas due to low compatibility, and a cured product with good release properties is provided.

Description

Fluoropolyether-based curable compositions and cured products, and electrical/electronic components

The present invention provides a fluoropolyether-based curable composition that provides a cured product that has durability against hydrofluoric acid or electrolyte solutions for lithium ion batteries, has no uncured areas due to low compatibility between components, and has good release properties, and this composition. It relates to a cured product and electrical/electronic components containing this cured product.

Fluoropolyether-based curable compositions using the addition reaction of alkenyl groups and hydrosilyl groups are known. For example, as a curable composition, a fluoropolyether compound (hereinafter also referred to as “base oil”) that has two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, and a silicon atom in one molecule. A composition containing a fluorinated organohydrogensiloxane having two or more hydrogen atoms directly connected to and a platinum group metal compound has been proposed (Patent Document 1: Japanese Patent Laid-Open No. 8-199070, Patent Document 2: Japanese Patent Laid-Open 2011- Bulletin No. 201940). Additionally, as a third component (adhesion improver), a composition in which self-adhesiveness is imparted by adding an organopolysiloxane having a hydrosilyl group, an epoxy group, and/or a trialkoxysilyl group to the composition has been proposed (Patent Document 3: Japanese Patent Laid-Open) Publication No. 9-95615, Patent Document 4: Japanese Patent Application Publication No. 2011-219692). The composition can be cured by heating for a short period of time, and the resulting cured product (fluoropolyether-based cured product) has excellent solvent resistance, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, and electrical properties, etc. It is used in various industrial fields that require this.

A fluoropolyether-based curable composition containing a fluorinated organohydrogensiloxane having two or more hydrogen atoms directly connected to a silicon atom in one molecule contains siloxane bonds that are unstable to acids, and is used for applications that require a high level of acid resistance. could not achieve sufficient performance. In particular, its durability against hydrofluoric acid was low, making it unsuitable for applications such as parts for semiconductor manufacturing equipment. In contrast, instead of this fluorinated organohydrogensiloxane, a fluoropolyether-based compound is used that does not contain a siloxane bond and has two or more hydrogen atoms directly connected to silicon atoms in one molecule. It has been proposed to improve the acid resistance of the cured product (Patent Document 5: Japanese Patent Laid-Open No. 2002-012769).

On the other hand, the fluorinated organohydrogensilane compound tends to occupy a large proportion of the total molecules of the non-fluorinated organic structure. This largely depends on the circumstances of the synthesis of the fluorinated organohydrogensilane compound. In this case, the short-chain perfluoroalkylene group lacks compatibility with the base oil. From this tendency, when a fluorinated organohydrogensilane compound is added to a fluoropolyether-based curable composition, the fluoropolyether-based curable composition becomes cloudy and the viscosity may increase. Additionally, the surface of the fluoropolyether-based cured product obtained from this fluoropolyether-based curable composition was also dotted with oil-like, uncured portions. Due to the presence of these uncured portions, the release properties of this fluoropolyether-based cured product are often impaired, and during the manufacturing process of articles containing this cured product, this cured product does not peel off from parts in the manufacturing equipment. This is undesirable because problems may occur that prevent manufacturing from proceeding smoothly.

Due to the recent growing interest in environmental issues, the development of products using lithium-ion batteries is actively underway worldwide. However, the fluoropolyether-based curable composition and its cured product containing a fluorinated organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule have low durability against electrolyte solutions for lithium ion batteries, It was found that application for this purpose was difficult. Also, instead of this fluorinated organohydrogensiloxane, a fluoropolyether-based curable composition containing a fluorinated organohydrogensilane compound that does not contain a siloxane bond and has two or more hydrogen atoms directly connected to silicon atoms in one molecule. As for the cured product, there was no knowledge regarding its durability in electrolyte solutions for lithium ion batteries, and it was unknown whether it could be applied to this application.

Japanese Patent Laid-open Publication No. 8-199070 Japanese Patent Application Publication No. 2011-201940 Japanese Patent Application Publication No. 9-95615 Japanese Patent Application Publication No. 2011-219692 Japanese Patent Application Publication No. 2002-012769

The present invention was made in consideration of the above circumstances, and provides a cured product that has durability against hydrofluoric acid and electrolyte solutions for lithium ion batteries, has no uncured areas due to low compatibility between the components, and has good release properties. The object is to provide a polyether-based curable composition, a cured product of the composition, and electrical/electronic components containing the cured product.

The present inventors conducted intensive studies to solve the above-described problems and as a result, as a curing agent for a fluoropolyether-based curable composition, a compound having a monovalent perfluoropolyether group and an alkenyl group was used as a curing agent with three or more hydrocarbons of a predetermined structure. It was found that when a fluorinated organohydrogensilane compound obtained by introducing it into an organohydrogensilane compound having a silyl group was used, it showed high compatibility with a perfluoropolyether compound having an alkenyl group as a base oil. In addition, the cured product obtained by curing the fluoropolyether-based curable composition obtained by adding this fluorinated organohydrogensilane compound exhibits durability against hydrofluoric acid and electrolyte solutions for lithium ion batteries, and has no uncured portion on the surface. It was discovered that it had good release properties, and the present invention was achieved.

Accordingly, the present invention provides the following fluoropolyether-based curable composition, a cured product obtained from the curable composition, and electrical/electronic components containing the cured product.

〔One〕

(A) Perfluoropolyether compound having two or more alkenyl groups in one molecule: 100 parts by mass,

(B) A fluorinated organohydrogensilane compound represented by the following general formula (1) and having two or more hydrosilyl groups: The hydrogen atom bonded to the silicon atom in component (B) relative to 1 mole of alkenyl group in component (A) an amount ranging from 0.1 to 2.5 moles, and

(Wherein, Rf is a monovalent perfluoropolyether group, A is a divalent organic group of 1 to 20 carbon atoms which may contain at least one selected from oxygen atom, nitrogen atom and silicon atom, and R is It is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, It is an organic group, and when x is 1, B has 2 or more diorganohydrosilyl groups. y is 1 or 2.)

(C) Platinum group metal catalyst: 0.1 to 2,000 ppm in terms of platinum group metal atoms based on the mass of component (A)

A fluoropolyether-based curable composition containing.

〔2〕

(A) The fluoropolyether-based curable composition according to [1], wherein the component is a perfluoropolyether compound represented by the following general formula (2).

[Wherein, A ¹ is a divalent organic group having 1 to 20 carbon atoms which may independently contain at least one selected from oxygen atom, nitrogen atom and silicon atom, B ¹ is a carbon atom or a silicon atom, is independently a hydrogen atom, a methyl group, or an alkenyl group having 2 to 8 carbon atoms, provided that at least ^two of Rf ¹ is a divalent perfluoropolyether group.]

〔3〕

(B) The fluoropolyether-based curable composition according to [1] or [2], wherein, in the component (1), Rf is a group represented by the following general formula (5).

(In the formula, D is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms, and a, b, c and d are each independently integers of 0 to 100, 2≤a+b+c+d≤100 , and e is an integer from 1 to 3. Each repeating unit shown in ( ) above may be randomly combined, and each of these units may be linear or branched.)

〔4〕

In the component (B), A in the general formula (1) is an alkylene group containing 1 to 12 carbon atoms, an alkylene group containing an arylene group with 6 to 8 carbon atoms, and each alkylene group is formed through a diorganosilylene group. A divalent group in which an alkylene group and an arylene group are bonded to each other through a diorganosilylene group, and in addition to these groups, at least one selected from an ether bonded oxygen atom, a secondary amino group, a tertiary amino group, and an amide bond. The fluoropolyether-based curable composition according to any one of [1] to [3], which is selected from divalent groups having one type.

〔5〕

In the component (B), A in the general formula (1) is a fluoro group described in any one of [1] to [4], which is any of the groups represented by the general formulas (6) to (9) below. Polyether-based curable composition.

(Wherein, ^{X 0} is a hydrogen atom, ^a methyl group, or an ethyl group, It is a phenyl group, R' is independently a methyl group or an ethyl group, f is an integer from 1 to 6, and t is 0 or 1. In addition, the bond with * is bonded to the Si atom in the general formula (1), and any Unmarked binding hands indicate binding to Rf.)

〔6〕

In the component (B), R in the general formula (1) is a fluorochemical according to any one of [1] to [5], wherein R is any one of a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, and a phenyl group. Low-polyether-based curable composition.

〔7〕

In the component (B), any of [1] to [6] wherein there are two or more consecutive silalkylene structures in the molecular chain between Rf of the general formula (1) and the diorganohydrosilyl group in B. The fluoropolyether-based curable composition described in one.

〔8〕

(B) The fluoropolyether-based curable composition according to any one of [1] to [7], wherein B in the general formula (1) is a group represented by the following general formula (10).

[In the formula, p is an integer of 1 to 6, q is an integer of 0 to 6, r is an integer of 1 to 3, R is the same as above, and E is a hydrogen atom or the following formula

(where R is the same as above, p' is an integer from 1 to 6, and q' is an integer from 0 to 6) (however, when E is a hydrogen atom, r is 1 am.). Each repeating unit displayed within ( ) to which p, q or p', q' is attached may be randomly combined.]

〔9〕

(B) The fluoropolyether-based curable composition according to any one of [1] to [8], wherein the component is selected from fluorine-containing organohydrogensilane compounds represented by the following formula.

(In the formula, b' is an integer from 2 to 100, c''' and d'' are each an integer from 1 to 99, c'''+d''=an integer from 2 to 100, Me is a methyl group , Et is an ethyl group, and Ph is a phenyl group. Each repeating unit shown in ( ) with c''' and d'' attached may be randomly combined.)

〔10〕

A cured product obtained from the fluoropolyether-based curable composition according to any one of [1] to [9].

〔11〕

Electrical/electronic components containing the cured product described in [10].

〔12〕

The electrical/electronic component according to [11], wherein the cured product is a gasket, packing, protective seal, or coating layer.

〔13〕

For automobiles, chemical plants, semiconductor manufacturing lines, analytical and physical chemistry equipment, residential environments, communication equipment, communication facilities, aircraft, railway vehicles, portable equipment, power storage devices, robots, or lithium ion. Electrical/electronic components described in [11] or [12] for batteries.

Since the fluoropolyether-based curable composition of the present invention contains a fluorinated organohydrogensilane compound of a specific structure that shows high compatibility with the base oil (A) component, this fluoropolyether-based curable composition Does not cause white clouding or thickening. In addition, by curing this composition, a fluoropolyether-based cured product can be obtained that has durability against hydrofluoric acid and electrolyte solutions for lithium ion batteries and is not dotted with oil-like uncured portions. Additionally, this fluoropolyether-based curable composition has excellent heat resistance, chemical resistance, and solvent resistance comparable to the fluoropolyether-based cured product obtained from the fluoropolyether-based curable composition described in Patent Documents 1 to 5.

Hereinafter, the present invention will be described in more detail.

[(A) Ingredient]

The perfluoropolyether compound as component (A) used in the fluoropolyether-based curable composition of the present invention has at least two alkenyl groups in one molecule, and is preferably represented by general formula (2) described later. Likewise, it has a divalent perfluoropolyether structure in the main chain, and acts as a main agent (base oil) in the fluoropolyether-based curable composition of the present invention.

In the present invention, the degree of polymerization (or molecular weight) of the polyfluoro compound, which reflects the number of repetitions of the perfluoroxyalkylene units constituting the perfluoropolyether structure of the main chain, is determined by, for example, using a fluorine-based solvent as a developing solvent. It can be obtained as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis. Additionally, the number average degree of polymerization (or number average molecular weight) of the perfluoropolyether compound described later can also be calculated from ¹⁹ F-NMR (the same applies hereinafter).

(A) Component is preferably a perfluoropolyether compound having a structure represented by the following general formula (2).

[Wherein, A ¹ is a divalent organic group having 1 to 20 carbon atoms which may independently contain at least one selected from oxygen atom, nitrogen atom and silicon atom, B ¹ is a carbon atom or a silicon atom, is independently a hydrogen atom, a methyl group, or an alkenyl group having 2 to 8 carbon atoms, provided that at least ^two of Rf ¹ is a divalent perfluoropolyether group.]

In the general formula (2), A ¹ is a divalent organic group having 1 to 20 carbon atoms which may independently contain at least one selected from oxygen atom, nitrogen atom and silicon atom, preferably an oxygen atom and a nitrogen atom. It is a divalent hydrocarbon group having 1 to 20 carbon atoms that may contain at least one type selected from an atom and a silicon atom, and examples of A ¹ include -(CH ₂ ) _f -*, -OCH ₂ -*, and -(CH ₂ ) _f OCH ₂ -*, -(CH ₂ ) _f -NX ² -CO-*, -(CH ₂ ) _f -O-CO-*, any selected from groups represented by the following general formulas (3) and (4) It is desirable to have one group. Additionally, the binding hand with * indicates that it binds to Rf ¹ , and the binding hand without any mark indicates that it binds to B ¹ .

(In the formula, X ¹ is independently a hydrogen atom, a fluorine atom, a ^methyl group, an ethyl group, or a trifluoromethyl group, .)

Examples of A ¹ include -CH ₂ -*, -CH ₂ CH ₂ CH ₂ -*, -OCH ₂ -*, -CH ₂ OCH ₂ -*, -(CH ₂ ) ₂ OCH ₂ -*, -(CH ₂ ) ₃ OCH ₂ -*, -CH ₂ -NH-CO-*, -CH ₂ -N(Me)-CO-*, -CH ₂ CH ₂ -NH-CO-*, -(CH ₂ ) ₃ - NH-CO-*, -(CH ₂ ) ₃ -N(Me)-CO-*, -(CH ₂ ) ₃ -N(Et)-CO-*, -(CH ₂ ) ₃ -N(CH(Me ) ₂ )-CO-*, -(CH ₂ ) ₃ -O-CO-*, the following general formulas (3A), (3B), (3C), (3D), (4A), (4B) and (4C) ), and among them, groups represented by the general formula (3A) or (4A) are preferable. Additionally, the binding hand with * indicates that it binds to Rf ¹ , and the binding hand without any mark indicates that it binds to B ¹ . Also, Me is a methyl group and Et is an ethyl group.

In the general formula (2), B ¹ is a carbon atom or a silicon atom.

Moreover, X is independently a hydrogen atom, a methyl group, or an alkenyl group having 2 to 8 carbon atoms, provided that at least two of Among the 6 This alkenyl group preferably has 2 to 8 carbon atoms, especially 2 to 6 carbon atoms, and has a CH ₂ =CH- structure at the terminal, for example, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexyl group. Examples include cenyl group, and among these, vinyl group and allyl group are preferable. When X is not an alkenyl group, when B ¹ is a carbon atom, it becomes either a hydrogen atom or a methyl group, and when B ¹ is a silicon atom, it becomes a methyl group.

In the general formula (2), Rf ¹ is a divalent perfluoropolyether group and contains a repeating unit of -C _g F _2g O- (where g is an integer of 1 to 6), For example, those expressed by the following formula (11) can be mentioned.

(In the formula, g is an integer of 1 to 6, and h is an integer of 5 to 600, preferably an integer of 10 to 400, more preferably an integer of 30 to 200.)

Examples of the repeating unit represented by the formula -C _g F _2g O- include units represented by the following formula.

Among these, the units expressed by the following formula are particularly suitable.

In addition, the repeating unit in the divalent perfluoropolyether group may be composed of one type of these alone, or may be composed of a combination of two or more types.

Moreover, it is preferable that the divalent perfluoropolyether group contains the structure of the following formula.

(In the formula, G is a fluorine atom or a trifluoromethyl group, and p1, q1 and r1 are p1≥0, q1≥0, 0≤p1+q1≤200, especially 2≤p1+q1≤150 and 0≤r1, respectively. ≤6 (when p1+q1=0, 1≤r1≤6), k1, a1, s1, t1, and u1 are 1≤k1≤3, 2≤a1≤6, 0≤s1≤, respectively. An integer that satisfies 100, 0≤t1≤100, 2≤s1+t1≤200, 0≤u1≤6, especially 2≤s1+t1≤150, 0≤u1≤4, 2≤s1+t1+u1≤150 , v1 and w1 are integers that satisfy 1≤v1≤100, 1≤w1≤100, and 2≤v1+w1≤200, respectively, z1 is an integer that satisfies 1≤z1≤200, and k1', a1' and a1'' are integers satisfying 1≤k1'≤3, 1≤a1'≤6, 1≤a1''≤6, and a1'≠a1'', respectively, and z1' is 1≤z1'≤200. It is an integer that satisfies. Each repeating unit displayed within ( ) attached to v1 and w1 may be randomly combined.)

In the general formula (2), specific examples of Rf ¹ include those represented by the following formula.

(In the formula, p1, q1, r1, v1, w1, z1, z1' are the same as above. s1' and t1' are integers from 1 to 100, respectively, and s1' + t1' = integers from 2 to 200. . t1'' is an integer from 2 to 100. Each repeating unit displayed within ( ) attached to v1 and w1 may be randomly combined.)

As the perfluoropolyether compound represented by the general formula (2), when B ¹ is a silicon atom, those represented by the following formula are particularly suitable. In addition, in the formula, Me is a methyl group and Et is an ethyl group.

(s1' and t1' are integers from 1 to 100, respectively, and s1'+t1'=integers from 2 to 200.)

(s1' and t1' are integers from 1 to 100, respectively, and s1'+t1'=integers from 2 to 200.)

(s1' and t1' are integers from 1 to 100, respectively, and s1'+t1'=integers from 2 to 200.)

(s1' and t1' are integers from 1 to 100, respectively, and s1'+t1'=integers from 2 to 200.)

(s1' and t1' are integers from 1 to 100, respectively, and s1'+t1'=integers from 2 to 200.)

As the perfluoropolyether compound represented by the general formula (2), when B ¹ is a carbon atom, one represented by the following formula is suitable.

(v1 and w1 are each integers from 1 to 100, and v1+w1 = integers from 2 to 200. Each repeating unit displayed within ( ) attached to v1 and w1 may be randomly combined.)

The amount of alkenyl groups contained in the perfluoropolyether compound as component (A) is preferably 0.002 to 0.3 mol/100g, and more preferably 0.008 to 0.12 mol/100g. If the amount of alkenyl groups contained in the perfluoropolyether compound is less than 0.002 mol/100g, it is not preferable because the degree of crosslinking may be insufficient and curing problems may occur, and if the amount of alkenyl groups contained in the perfluoropolyether compound is more than 0.3 mol/100g. This is not preferable because the mechanical properties of this cured product as a rubber elastomer may be damaged. In the present invention, the amount of alkenyl group can be measured by ¹ H-NMR (the same applies to the Examples).

The viscosity (23°C) of the perfluoropolyether compound as component (A) is within the range of 40 to 100,000 mPa·s, more preferably 50 to 50,000 mPa·s, and still more preferably 60 to 20,000 mPa·s. This is preferable because the cured product has appropriate physical properties when using the fluoropolyether-based curable composition of the present invention for sealing, potting, coating, impregnation, etc. Within the viscosity range, the most appropriate viscosity can be selected depending on the application. In the present invention, viscosity (23°C) can be measured with a rotational viscometer, etc. (e.g., BL type, BH type, BS type, corn plate type, rheometer, etc.) (hereinafter the same applies).

(A) Component can use these perfluoropolyether compounds individually 1 type or in combination of 2 or more types.

[(B) Ingredient]

Component (B) used in the fluoropolyether-based curable composition of the present invention is a fluorinated organohydrogensilane compound represented by the following general formula (1) and having two or more hydrosilyl groups, and specifically, hydrosilyl group. It is characterized as a compound having two or more groups, and all of the connections between silicon atoms are formed in a silicon alkylene structure (the alkylene group in the silicon alkylene structure may also be a partially fluorine-substituted fluorine-substituted alkylene group), and the siloxane It does not contain any combination.

(Wherein, Rf is a monovalent perfluoropolyether group, A is a divalent organic group of 1 to 20 carbon atoms which may contain at least one selected from oxygen atom, nitrogen atom and silicon atom, and R is It is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, It is an organic group, and when x is 1, B has 2 or more diorganohydrosilyl groups. y is 1 or 2.)

Rf in the general formula (1) is a monovalent perfluoropolyether group. Rf is introduced to provide compatibility with the base oil in the fluoropolyether-based curable composition (particularly, the thermosetting fluoropolyether-based composition). Compared to perfluoroalkyl groups, perfluoropolyether groups have a greater effect of providing compatibility with base oils by introducing them into organohydrogensilane compounds, and can provide fluoropolyether-based cured products with good properties. .

In particular, Rf in the general formula (1) is preferably a monovalent perfluoropolyether group represented by the following general formula (5).

(In the formula, D is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms, and a, b, c and d are each independently integers of 0 to 100, 2≤a+b+c+d≤100 , preferably a is an integer of 0 to 50, b is an integer of 0 to 50, c is an integer of 0 to 50, d is an integer of 0 to 50, 5≤a+b+c+d≤50, More preferably, a is an integer of 0 to 10, b is an integer of 0 to 40, c is an integer of 0 to 30, d is an integer of 0 to 30, and 6≤a+b+c+d≤40. Preferably, 7≤a+b+c+d≤30, and e is an integer of 1 to 3. Each repeating unit shown in ( ) may be randomly combined, and each of these units may be linear. It can be weather.)

In the general formula (5), D is a fluorine atom or a perfluoroxyalkyl group having 1 to 6 carbon atoms, and the perfluoroxyalkyl group having 1 to 6 carbon atoms is C _g F _2g+1 O- (g is 1 to 6 is represented by an integer of 6), and specifically, a group represented by the following formula is included.

D is preferably a fluorine atom.

In the general formula (5), when a+b+c+d is less than 2, it is not preferable because the compatibility between the fluorinated organohydrogensilane compound and the base oil may decrease. On the other hand, when a+b+c+d is greater than 100, the viscosity of the fluorinated organohydrogensilane compound increases, and at the same time, the viscosity of the thermosetting fluoropolyether-based composition to which the fluorinated organohydrogensilane compound is added increases. It is also undesirable because it becomes too high.

Examples of the monovalent perfluoropolyether group represented by the general formula (5) include the following.

(In the formula, g is an integer from 1 to 6, c' is an integer from 2 to 100, b' is an integer from 2 to 100, and e' is 2 or 3. c'' and d' are each 0 It is an integer of ~100, where c''+d' is an integer of 2~100, and a' is an integer of 2~100. Each repeating unit displayed within ( ) with c'' and d' attached is randomly combined. It can be done.)

In the general formula (1), A is a divalent organic group having 1 to 20 carbon atoms which may contain at least one selected from an oxygen atom, a nitrogen atom and a silicon atom, preferably an oxygen atom, a nitrogen atom and a silicon atom. It is a divalent hydrocarbon group with 1 to 20 carbon atoms that may contain at least one type selected from atoms, and an alkylene group with 1 to 12 carbon atoms, including an alkylene group with 1 to 12 carbon atoms and an arylene group with 6 to 8 carbon atoms (e.g. For example, alkylene and arylene groups with 8 to 20 carbon atoms), divalent groups in which alkylene groups with 1 to 10 carbon atoms are bonded to each other through diorganosilylene groups, and alkylene groups with 1 to 10 carbon atoms and aryl with 6 to 8 carbon atoms. A divalent group to which the lene group is bonded through a diorganosilylene group, and in addition to these groups, at least one type selected from an ether bonded oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond. A divalent group having a can be exemplified, and among them, at least one selected from an ether bonded oxygen atom, a secondary amino group (imino group), a tertiary amino group (substituted imino group), and an amide bond is included in the molecular chain. It is preferable that it is a divalent group. In addition, when A contains a silicon atom (diorganosilylene group), the silicon atom connected to this silicon atom (diorganosilylene group) and A is an alkylene group (preferably unsubstituted or fluorine-substituted alkyl having 1 to 12 carbon atoms). It is preferable to form a silalkylene structure connected through a lene group, more preferably an ethylene group.

Specifically, A is preferably represented by any of the following general formulas (6) to (9).

(Wherein, ^{X 0} is a hydrogen atom, ^a methyl group, or an ethyl group, It is a phenyl group, R' is independently a methyl group or an ethyl group, f is an integer from 1 to 6, and t is 0 or 1. In addition, the bond with * is bonded to the Si atom in the general formula (1), and any Unmarked binding hands indicate binding to Rf.)

Examples of structural examples of A represented by the above general formulas (6) to (9) include the following.

(In the formula, Me is a methyl group, and Et is an ethyl group. Additionally, the bond with * indicates that it bonds with the Si atom in the general formula (1), and the bond without any sign indicates that it bonds with Rf.)

R in the general formula (1) is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and specifically, is preferably a methyl group, ethyl group, isopropyl group, tertiary butyl group, or phenyl group, and is preferably a methyl group or an ethyl group. It is more preferable.

B in the general formula (1) has one or more diorganohydrosilyl groups and is preferably a monovalent organic group that forms a silalkylene structure with the connecting silicon atom, that is, two or more when x is 1. Typically, it has 2 to 5 diorganohydrosilyl groups, and when x is 2 or 3, it independently has at least 1, preferably 1 to 3 diorganohydrosilyl groups, and the connecting silicon atom and silalkylene It is a monovalent silicon-containing organic group that forms the structure, and does not contain a siloxane bond. In addition, the real alkylene structure is preferably one in which silicon atoms are connected to each other through an unsubstituted and/or fluorine-substituted alkylene group R ^A having 1 to 12 carbon atoms. Moreover, it is preferable that B has 1 or more silicon atoms, more preferably 1 to 6 silicon atoms, and even more preferably 1 to 4 silicon atoms. In formula (1), 1 to 3 B bonds to the silicon atom (x is an integer of 1 to 3), and preferably 2 or 3 B bonds to the silicon atom (preferably x is 2 or 3). ).

In addition, the continuous silalkylene structure in the molecular chain between Rf of the general formula (1) and the diorganohydrosilyl group in B (i.e. -A-Si-, -Si-(CH ₂ ) _{y -} in the formula It is preferable that the number of consecutive silalkylene bonds (-Si-R ^A -Si-)), including Si- and -Si-B, is 2 or more, and more preferably 2, 3, or 4.

B is preferably represented by the following general formula (10).

[In the formula, p is an integer of 1 to 6, preferably an integer of 1 to 4, q is an integer of 0 to 6, preferably an integer of 0 or 4 to 6, and r is an integer of 1 to 3. , R is the same as above, and E is a hydrogen atom or the formula below

A group represented by (where R is the same as above, p' is an integer of 1 to 6, preferably an integer of 1 to 4, and q' is an integer of 0 to 6, preferably 0 or 4 to It is an integer of 6.) (However, when E is a hydrogen atom, r is 1.) Each repeating unit displayed within ( ) to which p, q or p', q' is attached may be randomly combined.]

R in the general formula (10) is, like R in the general formula (1), a monovalent hydrocarbon group having 1 to 6 carbon atoms, including methyl, ethyl, propyl, isopropyl, tertiary butyl, Phenyl groups are particularly preferred.

Examples of B in the general formula (1) include the following.

(In the formula, Me is a methyl group, Et is an ethyl group, iPr is an isopropyl group, tBu is a tertiary butyl group, and Ph is a phenyl group.)

Examples of the fluorinated organohydrogensilane compound represented by the general formula (1) include the following.

(In the formula, b' is an integer from 2 to 100, c''' and d'' are each an integer from 1 to 99, c'''+d''=an integer from 2 to 100, Me is a methyl group , Et is an ethyl group, and Ph is a phenyl group. Each repeating unit shown in ( ) with c''' and d'' attached may be randomly combined.)

[Method for producing fluorinated organohydrogen silane compounds]

The method for producing the fluorinated organohydrogensilane compound represented by the general formula (1), which is the component (B), includes, for example, a fluorinated compound containing an alkenyl group (vinyl group) represented by the general formula (1A) below: By a hydrosilylation reaction using an organohydrosilane compound having at least three diorganohydrosilyl groups represented by the following general formula (1B), two or more diorganohydrosilyl groups are added to a fluorinated compound in a predetermined linking structure. It is desirable to have a process for introducing a group.

In general formula (1A), A ² is a divalent organic group having 1 to 18 carbon atoms that may contain at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom. The description of Rf, R, B, y, and x in the above general formulas (1A) and (1B) is common to the description of Rf, R, B, y, and x in the above general formula (1). That is, in the general formulas (1A) and (1B), Rf is a monovalent perfluoropolyether group, R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, x is an integer of 1 to 3, and B is a monovalent organic group that independently has one or more diorganohydrosilyl groups and forms a silalkylene structure with the connecting silicon atom. When x is 1, B has two or more diorganohydrosilyl groups. y is 1 or 2.

A ² is a divalent organic group (preferably a hydrocarbon group) having 1 to 18 carbon atoms which may contain at least one selected from oxygen atom, nitrogen atom and silicon atom, and is an alkylene group having 1 to 10 carbon atoms and 6 carbon atoms. Alkylene groups with 1 to 10 carbon atoms, including arylene groups with 8 to 10 carbon atoms (for example, alkylene and arylene groups with 6 to 18 carbon atoms), divalent groups in which a diorganosilylene group is bonded to an alkylene group with 1 to 10 carbon atoms. , a divalent group in which a diorganosilylene group is bonded to an arylene group of 6 to 8 carbon atoms, a divalent group in which an alkylene group of 1 to 10 carbon atoms is bonded to an alkylene group of 1 to 8 carbon atoms through a diorganosilylene group, A divalent group in which an alkylene group with 1 to 8 carbon atoms and an arylene group with 6 to 8 carbon atoms are bonded through a diorganosilylene group, and in addition to these groups, an ether bonded oxygen atom, a secondary amino group (imino group), and a tertiary amino group. (substituted imino group) and a divalent group having at least one type selected from an amide bond, among others, an ether bonded oxygen atom in the molecular chain, a secondary amino group (imino group), and a tertiary amino group (substituted imino group). It is preferable that it is a divalent group containing at least one type selected from amine bonds and amide bonds.

A ² is preferably represented by one of the following general formulas.

^{( In the} formula, ^{X 0 ,} It is an integer of ~4. The bond with * indicates that it bonds with the vinyl group of the general formula (1A), and the bond without any sign indicates that it bonds with Rf.)

Examples of structures of A ² represented by the above general formula include the following.

(In the formula, Me is a methyl group, and Et is an ethyl group. The bond with * indicates that it bonds with the vinyl group of the general formula (1A), and the bond without any sign indicates that it bonds with Rf.)

The manufacturing process (reaction formula) of a preferred method for producing a fluorinated organohydrogensilane compound is shown below.

The description of Rf, A, R, B, y, and x in the reaction formula shown in the above process is the same as the description of Rf, A, R, B, y, and x in the general formula (1) above. The description of A ² is the same as that of A ² in General Formula (1A) above. M is a metal catalyst.

In the above step, a fluorinated compound represented by the above general formula (1A) and having an alkenyl group (preferably a vinyl group or allyl group) at the terminal of the molecular chain, and a fluorinated compound represented by the above general formula (1B) and in the molecule A fluorinated organohydrogensilane compound represented by the general formula (1) is produced by subjecting an organohydrogensilane compound having at least three diorganohydrosilyl groups to a hydrosilylation reaction in the presence of a metal catalyst (M).

In the above reaction, as the fluorine-containing compound represented by the general formula (1A) and having an alkenyl group (preferably a vinyl group or an allyl group) at the terminal of the molecular chain, the following compounds can be used, for example.

(In the formula, b' is an integer from 2 to 100, c''' and d'' are each an integer from 1 to 99, c'''+d''=an integer from 2 to 100, Me is a methyl group and Et is an ethyl group. Each repeating unit displayed in ( ) with c''' and d'' attached may be randomly combined.)

As an organohydrosilane compound represented by the general formula (1B) and having at least three diorganohydrosilyl groups in the molecule, the following compounds can be used, for example.

(In the formula, Me is a methyl group, Et is an ethyl group, and Ph is a phenyl group.)

The amount of the fluorine-containing compound represented by the general formula (1A) and having an alkenyl group (preferably a vinyl group or an allyl group) at the terminal of the molecular chain to be used is determined by the amount of alkenyl groups of the fluorine-containing compound in the general formula (1A) The amount is 0.16 to 0.30 equivalents, preferably 0.20 to 0.25 equivalents, relative to the amount of hydrosilyl group of the compound represented by 1B). When the amount of alkenyl groups of this fluorine-containing compound is less than 0.16 equivalents relative to the amount of hydrosilyl groups of the compound represented by the general formula (1B), the resulting fluorinated organohydrogensilane compound is added to the fluoropolyether-based curable composition. This is undesirable because it may cause problems such as uncured portions dotting the surface of the cured product obtained by thermal curing, which may cause white turbidity or thickening. Moreover, if the amount of alkenyl groups in this fluorine-containing compound is more than 0.30 equivalents relative to the amount of hydrosilyl groups in the compound represented by the general formula (1A), the amount of hydrosilyl groups in the obtained fluorinated organohydrogensilane compound becomes too small, This is undesirable because it becomes difficult to cure the fluoropolyether-based curable composition.

In addition, the reaction process can rapidly progress hydrosilylation by adding M (metal catalyst). M is not particularly limited as long as it is a metal catalyst that can serve as a catalyst for hydrosilylation, but a compound containing a metal atom such as platinum, rhodium, ruthenium, or palladium can be suitably used. For example, complexes of chloroplatinic acid or chloroplatinic acid with olefins such as ethylene, complexes with alcohols or vinyl siloxanes, metal platinum supported on silica, alumina, carbon, etc., RhCl(PPh ₃ ) ₃ , RhCl(CO)(PPh ₃ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl(CO)(PPh ₃ ) ₂ , Pd(PPh ₃ ) ₄ , etc. may be exemplified. Also, in the above formula, Ph is a phenyl group. Among them, platinum compounds are particularly preferable.

When using these catalysts, if they are solid catalysts, they can be used in solid form. However, in order to proceed more quickly, it is preferable to use the metal catalyst dissolved in an appropriate solvent. When added, a fluorinated compound represented by the above general formula (1A) and having an alkenyl group (preferably a vinyl or allyl group) at the terminal of the molecular chain or a fluorinated compound represented by the above general formula (1B) and at least in the molecule. It is preferable to add dropwise after confirming that the inside of the system in which the organohydrosilane compound having three diorganohydrosilyl groups coexists is heated to a predetermined temperature. The predetermined temperature is preferably 50°C or higher, and more preferably 65°C or higher.

A fluorine-containing compound represented by the general formula (1A) and having an alkenyl group (preferably a vinyl or allyl group) at the terminal of the molecular chain, or a fluorinated compound represented by the general formula (1B) and at least three diorganos in the molecule. When the organohydrosilane compounds having a hydrosilyl group are solid or when the compounds do not dissolve each other, they may be dissolved in a small amount of an organic solvent and then M (metal catalyst) may be added. Solvents that can be used include benzene, toluene, xylene, and 1,3-bistrifluoromethylbenzene, and 1,3-bistrifluoromethylbenzene is preferred.

The amount of hydrosilyl groups in the fluorinated organohydrogensilane compound as component (B) is preferably 0.05 to 0.35 mol/100g, and more preferably 0.06 to 0.30 mol/100g. In the present invention, the amount of hydrosilyl group can be measured by ¹ H-NMR (the same applies to the Examples).

The mixing amount of the component (B) is such that the hydrogen atom (hydrosilyl group, i.e. Si-H group) bonded to the silicon atom in component (B) is equal to 1 mole of alkenyl groups such as vinyl and allyl groups in component (A). The amount is 0.1 to 2.5 mol, preferably 0.2 to 2 mol. If the hydrosilyl group is too small, the degree of crosslinking becomes insufficient, and as a result, a cured product cannot be obtained, and if the hydrosilyl group is too large, foaming occurs during curing.

In the method for producing the fluorinated organohydrogensilane compound that is component (B), the target product may be isolated after completion of the reaction. Additionally, to the extent that the characteristics of the present invention are not impaired, mixtures containing unreacted products or by-products can be used by removing the addition reaction catalyst. In any case, as long as the hydrosilyl group, that is, Si-H group, is contained in an amount of 0.1 to 2.5 mol, preferably 0.2 to 2 mol, per mole of alkenyl groups such as vinyl group and allyl group in component (A). do.

(B) Component may be used individually by one type of these fluorine-containing organohydrogensilane compounds, or may be used in combination of two or more types.

[(C)Component]

Component (C) used in the fluoropolyether-based curable composition of the present invention is a platinum group metal-based catalyst. This is a hydrosilylation reaction catalyst, which promotes the addition reaction between the alkenyl group in component (A) and the hydrosilyl group in component (B) and the optional adhesion improver or adhesion promoter described later. This hydrosilylation reaction catalyst is generally a noble metal compound, and since it is expensive, platinum or a platinum compound, which is relatively easy to obtain, is often used.

Examples of platinum compounds include chloroplatinic acid or complexes of chloroplatinic acid and olefins such as ethylene, complexes with alcohols or vinylsiloxanes, and metal platinum supported on silica, alumina, carbon, etc. As platinum group metal-based catalysts other than platinum compounds, rhodium, ruthenium, iridium, and palladium-based compounds are also known, for example, RhCl(PPh ₃ ) ₃ , RhCl(CO)(PPh ₃ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl Examples include (CO)(PPh ₃ ) ₂ and Pd(PPh ₃ ) ₄ . Also, in the above formula, Ph is a phenyl group.

When using these as catalysts, if they are solid catalysts, they can be used in solid form. However, in order to obtain a more uniform cured product, chloroplatinic acid or the complex is dissolved in an appropriate solvent to form the perfluoropolyether compound as component (A). It is desirable to use it interchangeably.

The amount of component (C) used may be a catalytic amount, but for example, it is preferable to mix 0.1 to 1,000 ppm (in terms of platinum group metal atoms) with respect to the mass of component (A), and 1 to 500 ppm is more preferable. (C) Component can be used individually or in combination of two or more types.

[Other ingredients]

In the fluoropolyether-based curable composition of the present invention, for the purpose of improving its practicality, in addition to the above-mentioned components (A) to (C), an adhesion improver (adhesion imparting agent), a plasticizer, a viscosity modifier, and a flexible agent are added. Various compounding agents such as imparting agents, hydrosilylation reaction catalyst control agents, inorganic fillers, adhesion promoters, and silane coupling agents can be added as needed. The mixing amount of these additives is arbitrary as long as it does not impair the purpose of the present invention, and does not impair the properties of the composition and the physical properties of the cured product.

The adhesion improver acts as an adhesion improver to develop self-adhesiveness in the fluoropolyether-based curable composition of the present invention by mixing it, and contains a hydrogen atom (Si-H group) bonded to a silicon atom in one molecule, It is an organohydrogenpolysiloxane compound having one or more epoxy groups and/or trialkoxysilyl groups each bonded to a silicon atom through a carbon atom or a carbon atom and an oxygen atom. In addition, since this adhesion improver has a molecular structure corresponding to fluorinated organohydrogen siloxane, it is difficult to maintain long-term self-adhesiveness to hydrofluoric acid or electrolyte solutions for lithium ion secondary batteries by using this adhesion improver. However, it is very effective in cases where initial self-adhesiveness is required, such as during the manufacturing process of an article having a cured product obtained from the fluoropolyether-based curable composition of the present invention.

In the above adhesion improver, one molecule further contains at least one selected from an oxygen atom, a nitrogen atom, a carbon atom and a silicon atom, and is bonded to a silicon atom through a divalent linking group, particularly containing a nitrogen atom and a carbon atom. A perfluoroalkyl group or monovalent perfluoropolyether group (perfluorooxy) bonded to a silicon atom through a divalent linking group, or bonded to a silicon atom through a divalent linking group containing a nitrogen atom, a carbon atom, and an oxygen atom. It is more preferable to have one or more alkyl groups). Examples of such perfluoroalkyl groups include groups represented by C _j F _2j+1 - (j is an integer of 1 to 10, preferably 3 to 7). Also, examples of the monovalent perfluoropolyether group include those similar to those exemplified by Rf in formula (1) shown in the component (B) above. In addition, the divalent linking group connecting the perfluoroalkyl group or monovalent perfluoropolyether group and the silicon atom is 2 having 1 to 20 carbon atoms, which may contain at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom. An organic group (preferably a hydrocarbon group) can be used.

The siloxane skeleton of the organohydrogenpolysiloxane compound of the adhesion improving agent may be cyclic, linear, branched, or the like, or may be a mixture of two or more of these, but is preferably cyclic. As the organohydrogenpolysiloxane compound of the adhesion improver, those represented by the following general formula can be used.

(In the formula, R ² is an unsubstituted or halogen-substituted monovalent hydrocarbon group, L ¹ is a monovalent perfluoropolyether group bonded to a silicon atom through a divalent linking group, and M ¹ is a carbon atom shown below or It is an epoxy group or trialkoxysilyl group bonded to a silicon atom through a carbon atom and an oxygen atom.w2 is preferably an integer satisfying 0≤w2≤50, more preferably an integer satisfying 0≤w2≤20, x2 is preferably an integer that satisfies 1≤x2≤50, more preferably an integer that satisfies 1≤x2≤20, y2 is preferably an integer that satisfies 0≤y2≤50, and more preferably is an integer that satisfies 1≤y2≤20, and z2 is preferably an integer that satisfies 1≤z2≤50, and more preferably is an integer that satisfies 1≤z2≤20. Each indicated in ( ) above Repeating units may be randomly combined.)

The unsubstituted or halogen-substituted monovalent hydrocarbon group for R ² preferably does not contain an aliphatic unsaturated bond and has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and is specifically a methyl group, an ethyl group, Alkyl groups such as propyl group, butyl group, hexyl group, cyclohexyl group, and octyl group; Aryl groups such as phenyl group and tolyl group; Examples include aralkyl groups such as benzyl group and phenylethyl group, and substituted monovalent hydrocarbon groups in which part or all of the hydrogen atoms of these groups are replaced with halogen atoms such as fluorine, and among these, methyl group is particularly preferable.

The L ¹ is a monovalent perfluoropolyether group bonded to a silicon atom through a divalent linking group, and is preferably represented by the general formula below.

-Z-Rf ²

[In the formula, Rf ² is a monovalent perfluoropolyether group, is the same as Rf in the general formula (1), and can be exemplified the same as those exemplified by Rf. Z is a divalent organic group (preferably a hydrocarbon group) having 1 to 20 carbon atoms which may contain at least one selected from oxygen atom, nitrogen atom and silicon atom.]

Examples of Z include -CH ₂ -*, -CH ₂ CH ₂ CH ₂ -*, -OCH ₂ -*, -CH ₂ OCH ₂ -*, -(CH ₂ ) ₂ OCH ₂ -*, -(CH ₂ ) ₃ OCH ₂ -*, -CH ₂ -NH-CO-*, -(CH ₂ ) ₃ -NH-CO-*, -(CH ₂ ) ₃ -N(Me)-CO-*, -(CH ₂ ) ₃ -N(Et)-CO-*, -(CH ₂ ) ₃ -N(CH(Me) ₂ )-CO-*, -CH ₂ -N(Ph)-CO-*, -(CH ₂ ) ₃ -O-CO-*, -CH ₂ OCH ₂ CH ₂ CH ₂ -Si(Me) ₂ -O-Si(Me) ₂ -(CH ₂ ) ₂ -*, -CO-N(Me)-Ph' -Si(Me) ₂ -(CH ₂ ) ₂ -*, -CO-N(CH ₂ )-Ph'-Si(CH ₂ ) ₂ -(CH ₂ ) ₂ -Si(CH ₂ ) ₂ -O-Si (CH ₂ ) ₂ -(CH ₂ ) ₂ -*, -CO-NH-Ph'-[Si(Me) ₂ -(CH ₂ ) ₂ ] ₃ -CH ₂ -*, -CO-N(Me)- Ph'-[Si(Me) ₂ -(CH ₂ ) ₂ ] ₃ -*, and groups represented by the following formulas include -(CH ₂ ) ₃ OCH ₂ -*, -(CH ₂ ) ₃ - NH-CO-*, a group represented by the following formula is preferred. Additionally, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and Ph' represents a phenylene group. Additionally, the bond with * indicates bonding with a monovalent perfluoropolyether group, and the bond without * indicates bonding with the silicon atom in organohydrogenpolysiloxane.

The M ¹ represents an epoxy group or trialkoxysilyl group bonded to a silicon atom through a carbon atom or a carbon atom and an oxygen atom, and specifically includes the following groups.

(In the formula, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, especially 1 to 5 carbon atoms, which may be interrupted by an oxygen atom (alkylene groups such as methylene group, ethylene group, propylene group, and cycloalkylene group such as cyclohexylene group) , oxyalkylene groups such as oxyethylene groups, oxypropylene groups, oxybutylene groups, etc., preferably -(CH ₂ ) ₃ OCH ₂ -*' (the bond with *' indicates that it bonds to an epoxy group)) indicates.)

-R ⁴ -Si(OR ⁵ ) ₃

(In the formula, R ⁴ represents a divalent hydrocarbon group (alkylene group such as methylene group, ethylene group, propylene group, etc.) with 1 to 10 carbon atoms, especially 1 to 4 carbon atoms, and R ⁵ independently represents 1 to 8 carbon atoms, In particular, it represents a monovalent hydrocarbon group having 1 to 4 carbon atoms (alkyl groups such as methyl, ethyl, propyl, butyl, etc.).

(In the formula, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, especially 1 to 4 carbon atoms (alkyl groups such as methyl, ethyl, propyl, butyl, etc.) , l represents an integer from 2 to 10.)

The organohydrogenpolysiloxane compound used as an adhesion improver is an organohydrogenpolysiloxane having three or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, and an aliphatic unsaturated group such as a vinyl group or an allyl group. A compound containing an epoxy group and/or a trialkoxysilyl group and, if necessary, a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or perfluorooxyalkyl group can be obtained by subjecting the compound to a partial addition reaction according to a conventional method. Additionally, the number of aliphatic unsaturated groups needs to be less than the number of Si-H groups.

When producing an organohydropolysiloxane compound used as an adhesion improver, the target substance may be isolated after completion of the reaction, or a mixture from which unreacted materials and addition reaction catalysts are simply removed may be used.

As an organohydrogenpolysiloxane compound used as an adhesion improver, specifically those represented by the following structural formula are exemplified. In addition, these compounds may be used individually or two or more types may be used together. In the formula below, Me represents a methyl group.

(In the formula, x2'=2 or 3, b1'=an integer of 2 to 20. Each repeating unit displayed in ( ) may be randomly combined.)

(In the formula, x2'=2 or 3, b1'=an integer of 2 to 20. Each repeating unit displayed in ( ) may be randomly combined.)

(In the formula, x2''=1 or 2, b1'=an integer of 2 to 20. Each repeating unit displayed in ( ) may be randomly combined.)

(In the formula, z2'=2 or 3, b1'=an integer of 2 to 20. Each repeating unit displayed in ( ) may be randomly combined.)

(In the formula, y2'=2 or 3, b1'=an integer of 2 to 20. Each repeating unit displayed in ( ) may be randomly combined.)

When blending the adhesion improver, the mixing amount is preferably an amount such that the hydrosilyl group (Si-H group) in the adhesion improver is 0.005 to 0.5 mole per mole of alkenyl group in component (A), more preferably. The amount is 0.01 to 0.2 mol, more preferably 0.05 to 0.1 mol.

As a plasticizer, viscosity modifier, and flexibility imparting agent, polyfluoromonoalkenyl compounds represented by the following general formula (12) and/or polyfluoro compounds represented by the following general formulas (13) and (14) can be used. there is.

[Wherein, Z ¹ is a divalent organic group (preferably a hydrocarbon group) having 1 to 20 carbon atoms which may contain at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, and p 2 is 0 or 1. , Rf ³ is a monovalent perfluoropolyether group represented by the general formula below.

(In the formula, f2 is an integer of 2 to 200, preferably an integer of 2 to 100, h2 is an integer of 1 to 3, and Rf ¹ in formula (2) in the component (A) to be used. It is smaller than the molecular weight.)]

[In the formula, Y ¹ is a group independently represented by the formula: C _k2 F _2k2+1 - (k2 is an integer of 1 to 3), c2 is an integer of 1 to 200, and It is smaller than the molecular weight of Rf ¹ in formula (2).]

(In the formula, Y ² is the same as Y ¹ above, d2 and e2 are each integers of 1 to 200, and is smaller than the molecular weight of Rf ¹ in formula (2) in the component (A) used. Above ( ) Each repeating unit displayed within may be randomly combined.)

In the general formula (12), Z ¹ is a divalent organic group (preferably a hydrocarbon group) having 1 to 20 carbon atoms that may contain at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, and In addition to the same thing as Z (divalent linking group) in the L ¹ structure, the ones shown below can be further exemplified (in the following and the example formulas for Z, the bond with * indicates that it bonds to Rf ³ and the bond without * represents bonding to a carbon atom. Also, Me represents a methyl group.)

Specific examples of the polyfluoromonoalkenyl compound represented by the general formula (12) include the following. Additionally, f2 below satisfies the above requirements.

Specific examples of polyfluoro compounds represented by the general formulas (13) and (14) include the following. Additionally, the following c2, d2, e2, and the sum of d2 and e2 satisfy the above requirements.

The viscosity (23°C) of the polyfluoromonoalkenyl compound of the formula (12) and the polyfluoro compound of the formulas (13) and (14) is preferably in the range of 2,000 to 50,000 mPa·s.

In addition, when mixing the polyfluoromonoalkenyl compound of the formula (12) and the polyfluoro compound of the formulas (13) and (14), the mixing amount is 1 to 300 parts by mass per 100 parts by mass of component (A). Parts by mass are preferable, more preferably 50 to 250 parts by mass.

Also, as a control agent for the hydrosilylation reaction catalyst, for example, ethynylcyclohexanol (aka: 1-ethynyl-1-hydroxycyclohexane), 3-methyl-1-butyn-3-ol, 3,5 -Acetylenic alcohols such as dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutinol, or chlorosilanes and acetylenic alcohols having the above-mentioned monovalent fluorine-containing substituent. Reactants, 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, triallyl isocyanurate, etc., or polyvinylsiloxane, organic phosphorus compounds, etc., By its addition, curing reactivity and storage stability can be appropriately maintained. The mixing amount of this control agent is arbitrary within the range that can provide the desired curing properties and storage stability.

Inorganic fillers include, for example, silica powder such as fumed silica (fumed silica or dry silica), precipitated silica (wet silica), spherical silica (fused silica), sol-gel silica, silica airgel, or the untreated surface of this silica powder. Various surface treatments obtained by hydrophobizing various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, etc. Reinforcing or semi-reinforcing fillers such as silica powder, quartz powder, fused quartz powder, diatomaceous earth, calcium carbonate, etc., oxidation Inorganic pigments such as titanium, iron oxide, carbon black, and cobalt aluminate, heat resistance improvers such as titanium oxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, and manganese carbonate, alumina, boron nitride, silicon carbide, A thermal conductivity imparting agent such as metal powder, a conductivity imparting agent such as carbon black, silver powder, or conductive zinc powder can be added.

When the adhesion promoter includes the adhesion improver, the adhesion promoter improves the adhesion imparting ability of the adhesion improver and promotes the development of self-adhesiveness of the cured product obtained by curing the fluoropolyether-based curable composition of the present invention. It is for. In particular, carboxylic acid anhydride can be suitably used.

Examples of the carboxylic acid anhydride include carboxylic acid anhydride that is solid at 23°C. Specifically, the following compounds are exemplified. In the formula below, Me represents a methyl group.

In addition, the carboxylic acid anhydride includes a hydrogen atom directly bonded to a silicon atom in one molecule, and a perfluorocarbon group bonded to a silicon atom through a divalent hydrocarbon group that may contain at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom. It may be a cyclic organopolysiloxane (i.e., a fluorinated organopolysiloxane-modified anhydrous carboxylic acid compound) having an alkyl group or perfluorooxyalkyl group and a cyclic anhydrous carboxylic acid residue bonded to a silicon atom through a divalent hydrocarbon group. Examples of such compounds include those represented by the following general formula (15). In addition, since this fluorinated organopolysiloxane-modified anhydrous carboxylic acid compound has a molecular structure corresponding to fluorinated organohydrogen siloxane, the use of this compound provides long-term self-adhesion to hydrofluoric acid and electrolytes for lithium ion secondary batteries, etc. Although it is difficult to maintain the adhesive properties, it is very effective in cases where initial self-adhesiveness is required, such as during the manufacturing process of an article having a cured product obtained from the fluoropolyether-based curable composition of the present invention.

(In the formula, L ² is independently a monovalent perfluoropolyether group bonded to a silicon atom through a divalent hydrocarbon group, J is independently a cyclic anhydrous carboxylic acid residue bonded to a silicon atom through a divalent hydrocarbon group, and R ⁸ is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group, t2 is an integer of 1 to 6, u2 is an integer of 1 to 4, v2 is an integer of 1 to 4, and t2+u2+v2 is an integer of 4 to 10. It is an integer. Each repeating unit displayed in ( ) above may be randomly combined.)

In the formula (15), L ² is a monovalent perfluoropolyether group bonded to a silicon atom through a divalent hydrocarbon group, and examples thereof include the same groups as L ¹ above. These are groups introduced from the viewpoint of compatibility with component (A), dispersibility, and uniformity after curing.

Moreover, in the above formula (15), R ⁸ is an unsubstituted or halogen-substituted monovalent hydrocarbon group, and examples thereof include the same groups as R ² described above, with methyl and ethyl groups being preferred.

In the above formula (15), J is a cyclic anhydride carboxylic acid residue bonded to a silicon atom through a divalent hydrocarbon group, and specifically includes a group represented by the following general formula.

In the above formula, R ⁹ is a divalent hydrocarbon group having 2 to 15 carbon atoms, and specific examples thereof include ethylene group, propylene group, butylene group, and among these, propylene group is preferable.

Also, in the above equation (15), t2 is an integer of 1 to 6, preferably an integer of 2 to 5, u2 is an integer of 1 to 4, preferably an integer of 1 to 3, and v2 is an integer of 1 to 4. , preferably an integer of 1 to 3, and t2+u2+v2 is an integer of 4 to 10, preferably an integer of 4 to 8. However, the arrangement order of the ((H)(R ⁸ )SiO) unit, ((L ² )(R ⁸ )SiO) unit, and ((J)(R ⁸ )SiO) unit is random.

Examples of cyclic organopolysiloxanes represented by the general formula (15) include the following compounds. In the formula below, Me represents a methyl group.

(In the formula, t2'=2 or 3, b2'=an integer of 2~20.)

(In the formula, v2'=2 or 3, b2'=an integer of 2~20.)

These adhesion promoters may be used individually, or two or more types may be used in combination. At that time, the solid carboxylic acid anhydride and the above-mentioned cyclic organopolysiloxane (fluorinated organopolysiloxane-modified anhydrous carboxylic acid compound) may be used together at 23°C.

When mixing an adhesion promoter, the mixing amount is preferably 0.01 to 2 parts by mass, and more preferably 0.05 to 1 part by mass, per 100 parts by mass of component (A). Moreover, it is preferable that the hydrosilyl group (Si-H group) in the adhesion promoter is 0.005 to 0.5 mol, especially 0.05 to 0.1 mol, per mole of alkenyl group in component (A).

Additionally, the total of hydrosilyl groups contained in the composition (particularly, the total of hydrosilyl groups in component (B), the adhesion improver and the adhesion promoter) per 1 mole of alkenyl groups in component (A) is 0.1 to 2.5 mol, especially 0.2 mol. ~2 moles is preferred.

[Method for producing fluoropolyether-based curable composition]

The method for producing the fluoropolyether-based curable composition of the present invention is not particularly limited, and it can be produced by mixing and folding the above components. Specifically, the fluoropolyether-based curable composition of the present invention is made by mixing the above-mentioned components (A) to (C) and other optional components in a mixing device such as a planetary mixer, Ross mixer, or Hobart mixer, and, if necessary, a kneader. It can be manufactured by uniformly mixing using a kneading device such as a three-roll roll.

Additionally, it may be used as a composition of two agents and mixed at the time of use.

The prepared fluoropolyether-based curable composition can be cured at room temperature depending on the type of catalyst of component (C), but it is better to heat it to accelerate curing. It is desirable to cure it at ℃ or higher, preferably at 100 to 200 ℃ for a period of several minutes to several hours.

In addition, when using the fluoropolyether-based curable composition of the present invention, depending on the use and purpose, this composition may be dissolved in an appropriate fluorine-based solvent, such as 1,3-bis(trifluoromethyl)benzene or fluorine nut (3M). It may be used by dissolving it in (manufactured by the company), perfluorobutyl methyl ether, perfluorobutyl ethyl ether, etc. at the desired concentration. In particular, it is preferable to use a solvent for thin film coating applications.

The fluoropolyether-based curable composition of the present invention is suitable for use in automobiles, chemical plants, semiconductor manufacturing lines, analytical and physical chemistry equipment, residential environments, communication equipment, communication facilities, aircraft, railway vehicles, and portable equipment. It is preferable to use it as electrical/electronic components such as batteries, power storage devices, robots, or lithium ion batteries.

Particularly preferred are electrical/electronic components using the cured product of the fluoropolyether-based curable composition of the present invention as a gasket, packing, protective seal, or coating layer.

(Example)

Hereinafter, the present invention will be described in detail by showing synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following examples, Me in the formula represents a methyl group, and part represents a mass part. In addition, the number average molecular weight was determined as the number average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis using AK-225 (manufactured by Asahi Glass), a fluorine-based solvent, as a developing solvent. Viscosity (23°C) represents the value measured based on the rotational viscometer method of viscosity testing specified in JIS K6249.

·Synthesis of fluorinated organohydrogen silane compounds

[Synthesis Example 1]

Organohydrogensilane compound represented by the following formula (16) in a 1L flask (hydrosilyl group weight 0.616 mol/100 g)

150 g and a compound represented by the following formula (17) (vinyl group amount 0.0681 mol/100 g)

339 g and 91 g of 1,3-bistrifluoromethylbenzene were introduced and nitrogen was substituted.

After raising the temperature to 70°C, 0.16 g of a toluene solution (platinum concentration 0.5% by mass) of the (C1) platinum-divinyltetramethyldisiloxane complex was added dropwise, and the mixture was stirred at 85°C for 1 hour. The reaction solution was poured and concentrated under reduced pressure. The obtained residue was dissolved in FC-3283 (524 g), stirred with 9.10 g of activated carbon (trade name: Shirasagi AS, manufactured by Osaka Gas Chemical Co., Ltd.) for 1 hour, and then filtered. Activated carbon (9.10 g) was added to the obtained solution, stirred for 1 hour, and then filtered.

The main component was extracted from the obtained solution by preparative liquid chromatography, and then concentrated under reduced pressure to obtain a compound represented by the following formula (18) (hydrosilyl group weight 0.143 mol/100 g)

376g was obtained. ^{The 1} H-NMR spectrum of the obtained product showed the following signals: δ7.86-6.55 (m, 4H), 4.38-3.64 (m, 3H), 3.15 (s, 3H), 2.46-1.48 (br, 4H), 1.18 ~-0.91 (m, 52H) was confirmed, and the production of the compound represented by the above formula (18) was confirmed.

[Synthesis Example 2]

Instead of the compound represented by the above formula (17), a compound represented by the following formula (19) (vinyl group amount 0.0228 mol/100g)

Except for using 1,012 g, the same operation as Synthesis Example 1 was performed to produce a compound represented by the following formula (20) (hydrosilyl group amount: 0.0682 mol/100 g).

741g was obtained. ^{The 1} H-NMR spectrum of the obtained product showed the following signals: δ7.68~6.36(m, 4H), 4.21~3.44(s, 3H), 3.03(s, 3H), 2.29~1.41(br, 4H), 1.13 ~-0.98 (m, 52H) was confirmed, and the production of the compound represented by the above formula (20) was confirmed.

[Synthesis Example 3]

Instead of the compound represented by the above formula (16), a compound represented by the following formula (21) (hydrosilyl group amount 1.09 mol/100g)

Except for using 85 g, the same operation as Synthesis Example 1 was performed to produce a compound represented by the following formula (22) (hydrosilyl group amount: 0.247 mol/100 g).

323g was obtained. ^{The 1H} -NMR spectrum of the obtained product showed the following signals: δ7.85~6.55(m, 4H), 4.29~3.51(m, 5H), 3.15(s, 3H), 1.23~-0.91(m, 62H). This confirmed the production of the compound represented by the above formula (22).

[Synthesis Example 4]

A compound represented by the following formula (23) instead of the compound represented by the above formula (17) (vinyl group amount 0.0873 mol/100g)

(average of m+n=12, m:n=0.98:1)

Except for using 264 g, the same operation as Synthesis Example 1 was performed to obtain a compound represented by the following formula (24) (hydrosilyl group amount: 0.169 mol/100 g).

(average of m+n=12, m:n=0.98:1)

317g was obtained. In the ¹ H-NMR spectrum of the obtained product, the following signals: δ6.89~6.61 (s, 1H), 4.39~3.66 (m, 3H), 3.41~3.07 (m, 2H), 2.46~1.47 (br, 4H) , 1.74 to 1.39 (m, 2H), 1.18 to -0.90 (m, 44H) were confirmed, and the production of the compound represented by the above formula (24) was confirmed.

<Preparation of fluoropolyether-based curable composition, confirmation of compatibility of component (B) and component (A) (base oil)>

[Example 1]

(A1) 100 parts of a polymer represented by the following formula (25) (number average molecular weight 15,550, viscosity 10,900 mPa·s, vinyl group weight 0.012 mol/100g), (C1) a toluene solution of platinum-divinyltetramethyldisiloxane complex. (Platinum concentration 0.5% by mass) 0.1 part, 0.07 parts of the compound represented by the following formula (26), (B1) 9.74 parts of the compound represented by the following formula (18) obtained in Synthesis Example 1 (hydrosilyl group amount 0.143 mol/100g) were added and mixed to prepare a curable composition, which was obtained as a transparent oil. From this point, it was shown that the compatibility of component (B1) and component (A1) was high.

(In the formula, m and n are integers greater than or equal to 1, and the average value of m+n is 90.)

[Example 2]

In Example 1, instead of (A1) the polymer represented by the above formula (25), (A2) the polymer represented by the following formula (27) (number average molecular weight 15,630, viscosity 11,000 mPa·s, vinyl base weight 0.012 mol/100 g) ) 100 parts were used, and other than that, a curable composition was prepared in the same manner as in Example 1, and was obtained as a transparent oil. From this point, it was shown that the compatibility of component (B1) and component (A2) was high.

(In the formula, m and n are integers greater than or equal to 1, and the average value of m+n is 90.)

[Example 3]

In Example 1, instead of (A1) the polymer represented by the above formula (25), (A3) the polymer represented by the following formula (28) (number average molecular weight 3,350, viscosity 60 mPa·s, vinyl base weight 0.031 mol/100g) A curable composition was prepared in the same manner as in Example 1 except that 100 parts (B1) were used, and 25.16 parts of the compound represented by the above formula (18) was obtained as a transparent oil. From this point, it was shown that the compatibility of component (B1) and component (A3) was high.

(m:n=0.98:1, average of m+n=34)

[Example 4]

In Example 1, (B1) instead of the compound represented by the above formula (18), (B2) the compound represented by the following formula (20) obtained in Synthesis Example 2 (hydrosilyl group amount: 0.0682 mol/100 g) 20.42 parts A curable composition was prepared in the same manner as in Example 1 except that, and obtained as a transparent oil. From this point, it was shown that the compatibility of component (B2) and component (A1) was high.

[Example 5]

In Example 1, instead of (B1) the compound represented by the above formula (18), 5.73 parts of (B3) the compound represented by the following formula (22) obtained in Synthesis Example 3 (hydrosilyl group amount: 0.247 mol/100g) was used. A curable composition was prepared in the same manner as in Example 1, and was obtained as a transparent oil. From this point, it was shown that the compatibility of component (B3) and component (A1) was high.

[Example 6]

In Example 1, (B1) instead of the compound represented by the above formula (18), 8.24 parts of (B4) the compound represented by the following formula (24) obtained in Synthesis Example 4 (hydrosilyl group amount: 0.169 mol/100g) was used. A curable composition was prepared in the same manner as in Example 1, and was obtained as a transparent oil. From this point, it was shown that the compatibility of component (B4) and component (A1) was high.

(m:n=0.98:1, average of m+n=12)

[Example 7]

In Example 1, (B1) instead of the compound represented by the above formula (18), (B1) was obtained in the same manner except that the main component was not extracted from the solution obtained in Synthesis Example 1 by preparative liquid chromatography and concentrated under reduced pressure. B5) A mixture of a compound represented by the above formula (18) and a compound represented by the following formulas (29), (30), (31) and (32) (mass ratio: (18)/(29)/(30)/ (31)/(32)=80:9:6:1:4, hydrosilyl group amount: 0.145 mol/100 g) 9.61 parts were used, and other than that, a curable composition was prepared in the same manner as in Example 1, and obtained as a transparent oil. lost. From this point, it was shown that the compatibility of component (B5) and component (A1) was high.

[Comparative Example 1]

In Example 1, instead of (B1) the compound represented by the formula (18), 2.26 parts of (B6) the compound represented by the formula (32) (hydrosilyl group amount 0.616 mol/100 g) was used, and in the other examples, A curable composition was prepared in the same manner as in 1, and was obtained as a cloudy oil. From this point, it was shown that the compatibility of component (B6) and component (A1) was low.

[Comparative Example 2]

In Example 1, instead of (B1) the compound represented by the above formula (18), (B7) the compound represented by the following formula (33) (Patent Document 5: described in Example 1 of Japanese Patent Application Publication No. 2002-012769 A curable composition was prepared in the same manner as in Example 1 except that 3.52 parts (compound, hydrosilyl group amount: 0.408 mol/100 g) were used, and a white cloudy oil was obtained. In this regard, it was shown that the compatibility of component (B7) and component (A1) was low.

[Comparative Example 3]

In Example 1, instead of (B1) the compound represented by the formula (18), 3.54 parts of (B8) the compound represented by the formula (34) (hydrosilyl group amount 0.394 mol/100 g) was used, and other than that, A curable composition was prepared in the same manner as in 1, and was obtained as a transparent oil. From this point, it was shown that component (B8) and component (A1) had high compatibility.

<Confirmation of the presence or absence of oil-like components (uncured portion) on the surface of the fluoropolyether-based cured product and evaluation of the release property of the cured product>

The fluoropolyether-based curable composition prepared in Examples 1 to 7 and Comparative Examples 1 to 3 was poured into a 2 mm thick stainless steel mold placed on a Teflon (registered trademark, hereinafter the same) sheet. After sandwiching it with a separate Teflon sheet, press cure was performed at 150°C/10 minutes. After press cure, the 2 mm thick stainless steel mold was removed and the release properties of the obtained fluoropolyether-based cured product and the remaining oil phase components on the surface of the cured product were evaluated according to the following evaluation criteria. The results are shown in Table 1 along with the appearance of the fluoropolyether-based curable composition.

[Evaluation standard]

○: The cured product could be easily removed from the Teflon sheet without damaging it, and no oily component remained on the surface of the removed cured product.

×: It was difficult to remove the cured product from the Teflon sheet without damaging it, and residual oil-like components were observed on the surface of the removed cured product.

In the fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Example 3, dots of uncured oil-like components were not observed on the surface of the cured product. This is because component (B) contained in the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Example 3 shows high compatibility with component (A), so that almost all of component (B) and component (A) This is because it reacted. Additionally, since the cured product could be easily removed from the Teflon sheet after press cure, it was confirmed that there was no problem with release properties. On the other hand, dots of uncured oil-like components were confirmed on the surface of the fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Comparative Examples 1 and 2. This is because the components (B6) and (B7) have insufficient compatibility with the component (A), and the reaction with the component (A) during heat curing is insufficient. Therefore, the unreacted product forms the fluoropolyether as an oil component. It is thought that it remained on the surface of the system hardened cargo. In addition, the cured product adhered to the Teflon sheet due to the press cure, resulting in low release properties, such as the cured product breaking or missing when peeled off from the Teflon sheet.

The fluoropolyether-based cured product obtained above was post-cured at 200°C/4 hours, and then heat resistance, chemical resistance, solvent resistance, and electrolyte solution resistance were evaluated. The results are shown in Tables 2 to 5.

<Heat resistance>

The physical properties of the fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated in accordance with JIS K 6249. Next, the fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were left in an oven at 150°C for 7 days and then cured in accordance with JIS K 6249. By evaluating the physical properties of water, the change in hardness, change in tensile strength (%), and change in elongation when cut (%) were calculated using the following calculation formula. The results are shown in Table 2.

Hardness change = (Hardness of cured product after 150℃/7 days) - (Initial hardness of cured product)

Tensile strength change rate (%) = ((tensile strength of cured product after 150℃/7 days) - (initial tensile strength of cured product)) / (initial tensile strength of cured product) × 100

Elongation change rate upon cutting (%) = ((Height upon cutting of the cured product after 150°C/7 days) - (Elongation upon initial cutting of the cured material))/(Elongation upon initial cutting of the cured product) x 100

<Chemical resistance>

The fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were mixed with concentrated hydrochloric acid, concentrated sulfuric acid, concentrated hydrofluoric acid, trifluoroacetic acid, and 40 mass% KOH at 20°C. (Potassium hydroxide) was immersed in an aqueous solution for 3 days, and the change in hardness was measured based on the hardness before immersion. The method for calculating the change in hardness used the same formula as in the heat resistance test. The results are shown in Table 3.

From the results in Table 3, it was confirmed that the cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 and 2 had excellent durability against all of the above chemicals. On the other hand, it was confirmed that the cured product obtained from the fluoropolyether-based curable composition of Comparative Example 3 had insufficient durability against concentrated hydrofluoric acid and trifluoroacetic acid.

<Solvent resistance>

Using the fluoropolyether-based cured products (cured product samples) obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3, various organic solvents shown in Table 4 were added in accordance with JIS K 6258. An immersion test (immersion time: 70 hours) was conducted, and the volume change rate (%) before and after immersion was measured to evaluate solvent swelling properties. The results are shown in Table 4.

*1) IPA: Isopropyl alcohol

*2) MEK: Methyl ethyl ketone

*3) THF: Tetrahydrofuran

From the results in Table 4, the cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7, like the cured products obtained from the curable fluoropolyether-based curable compositions of Comparative Examples 1 to 3, were soluble in all of the above solvents. It was confirmed that it has excellent durability.

<Electrostatic resistance>

The fluoropolyether-based cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were immersed in an electrolyte solution for lithium ion batteries (manufactured by Kishida Chemical Co., Ltd.) at 80°C for 3 days. Based on the changes in hardness, stickiness, and appearance of the cured product before and after, the degree of deterioration of the cured product was evaluated according to the following evaluation criteria.

[Evaluation standard]

〔Hardness〕

○: Little change in hardness was observed before and after immersion in the electrolyte solution for lithium ion batteries.

×: A significant decrease in hardness was observed due to immersion in the electrolyte solution for lithium ion batteries.

〔Stickness〕

○: There was no change in the stickiness of the surface of the cured product due to immersion in the electrolyte solution for lithium ion batteries.

×: The surface of the cured product became sticky due to immersion in the electrolyte solution for lithium ion batteries.

〔Exterior〕

○: Little change in appearance was observed before and after immersion in the electrolyte solution for lithium ion batteries.

×: Swelling, deformation, and decomposition of the cured product were observed by immersion in the electrolyte solution for lithium ion batteries.

The cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 and Comparative Examples 1 and 2 showed little change in hardness, surface stickiness, and appearance before and after immersion in the electrolyte solution for lithium ion batteries. In this regard, it was found that the composition and cured product can be applied to lithium ion battery applications. On the other hand, the cured product obtained from the fluoropolyether-based curable composition of Comparative Example 3 swelled when immersed in an electrolyte solution for lithium ion batteries, and changes such as surface decomposition were confirmed. Also, when both ends of this hardened material were pulled, it simply broke.

From the above results, it can be seen that the cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 7 have both durability and release properties against hydrofluoric acid and electrolyte solutions for lithium ion batteries, and demonstrate the effect of the present invention.

Claims (13)

(A) Perfluoropolyether compound having two or more alkenyl groups in one molecule: 100 parts by mass,
(B) A fluorinated organohydrogensilane compound represented by the following general formula (1) and having two or more hydrosilyl groups: The hydrogen atom bonded to the silicon atom in component (B) relative to 1 mole of alkenyl group in component (A) an amount ranging from 0.1 to 2.5 moles, and

(Wherein, Rf is a monovalent perfluoropolyether group, A is a divalent organic group of 1 to 20 carbon atoms which may contain at least one selected from oxygen atom, nitrogen atom and silicon atom, and R is It is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, It is an organic group, and when x is 1, B has 2 or more diorganohydrosilyl groups. y is 1 or 2.)
(C) Platinum group metal catalyst: 0.1 to 2,000 ppm in terms of platinum group metal atoms based on the mass of component (A)
A fluoropolyether-based curable composition containing. The fluoropolyether-based curable composition according to claim 1, wherein component (A) is a perfluoropolyether compound represented by the following general formula (2).

[Wherein, A ¹ is a divalent organic group having 1 to 20 carbon atoms which may independently contain at least one selected from oxygen atom, nitrogen atom and silicon atom, B ¹ is a carbon atom or a silicon atom, is independently a hydrogen atom, a methyl group, or an alkenyl group having 2 to 8 carbon atoms, provided that at least ^two of Rf ¹ is a divalent perfluoropolyether group.] The fluoropolyether-based curable composition according to claim 1 or 2, wherein in component (B), Rf in the general formula (1) is a group represented by the following general formula (5).

(In the formula, D is a fluorine atom or a perfluorooxyalkyl group having 1 to 6 carbon atoms, and a, b, c and d are each independently integers of 0 to 100, 2≤a+b+c+d≤100 , and e is an integer from 1 to 3. Each repeating unit shown in ( ) above may be randomly combined, and each of these units may be linear or branched.) The component (B) according to any one of claims 1 to 3, wherein A in the general formula (1) contains an alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 8 carbon atoms. an alkylene group, a divalent group in which the alkylene groups are bonded to each other through a diorganosilylene group, a divalent group in which an alkylene group and an arylene group are bonded to each other through a diorganosilylene group, and an ether-bonded oxygen atom in addition to these groups, A fluoropolyether-based curable composition selected from a divalent group having at least one type selected from a secondary amino group, a tertiary amino group, and an amide bond. The method according to any one of claims 1 to 4, wherein in component (B), A in the general formula (1) is any one of groups represented by the following general formulas (6) to (9): Fluoropolyether-based curable composition.

(Wherein, ^{X 0} is a hydrogen atom, ^a methyl group, or an ethyl group, It is a phenyl group, R' is independently a methyl group or an ethyl group, f is an integer from 1 to 6, and t is 0 or 1. In addition, the bond with * is bonded to the Si atom in the general formula (1), and any Unmarked binding hands indicate binding to Rf.) The method according to any one of claims 1 to 5, wherein in the component (B), R in the general formula (1) is any one of a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, and a phenyl group. Phosphorus fluoropolyether-based curable composition. The component (B) according to any one of claims 1 to 6, wherein the silalkylene structure in the molecular chain between Rf of the general formula (1) and the diorganohydrosilyl group in B is Two or more fluoropolyether-based curable compositions in succession. The fluoropolyether-based curable composition according to any one of claims 1 to 7, wherein in component (B), B in the general formula (1) is a group represented by the following general formula (10).

[In the formula, p is an integer of 1 to 6, q is an integer of 0 to 6, r is an integer of 1 to 3, R is the same as above, and E is a hydrogen atom or the following formula

(where R is the same as above, p' is an integer from 1 to 6, and q' is an integer from 0 to 6) (however, when E is a hydrogen atom, r is 1 am.). Each repeating unit displayed within ( ) to which p, q or p', q' is attached may be randomly combined.] The fluoropolyether-based curable composition according to any one of claims 1 to 8, wherein component (B) is selected from fluorinated organohydrogensilane compounds represented by the following formula.






(In the formula, b' is an integer from 2 to 100, c''' and d'' are each an integer from 1 to 99, c'''+d''=an integer from 2 to 100, Me is a methyl group , Et is an ethyl group, and Ph is a phenyl group. Each repeating unit shown in ( ) with c''' and d'' attached may be randomly combined.) A cured product obtained from the fluoropolyether-based curable composition according to any one of claims 1 to 9. Electrical/electronic components containing the hardened product of claim 10. The electrical/electronic component according to claim 11, wherein the cured product is a gasket, packing, protective seal, or coating layer. According to claim 11 or 12, for use in automobiles, chemical plants, semiconductor manufacturing lines, analytical and physical chemistry equipment, residential environments, communication equipment, communication facilities, aircraft, railway vehicles, portable equipment, Electrical and electronic components for power storage devices, robots, or lithium-ion batteries.